CN108545720A - A method of using shrimp and crab shells porous charcoal be raw graphite - Google Patents
A method of using shrimp and crab shells porous charcoal be raw graphite Download PDFInfo
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- CN108545720A CN108545720A CN201810430017.9A CN201810430017A CN108545720A CN 108545720 A CN108545720 A CN 108545720A CN 201810430017 A CN201810430017 A CN 201810430017A CN 108545720 A CN108545720 A CN 108545720A
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The present invention relates to graphenes and graphene oxide preparation field, more particularly to it is a kind of using the method that shrimp and crab shells porous charcoal is raw graphite, shrimp and crab shells porous charcoal is first crushed look over so as to check sieve, the porous powdered carbon of shrimp and crab shells and potassium carbonate by this method, sodium carbonate and zinc carbonate are used alone, or mutually mixed use；Under the conditions of nitrogen atmosphere, it is placed in graphitizing furnace；Control heating, heat preservation and slow cooling；It by gained graphitized products, is washed, then is washed with deionized with dilute hydrochloric acid, it is dry to obtain shrimp and crab shells porous charcoal graphitized products.The method of the present invention is simple, and strong acid and highly basic are not used in production process, reduces sewage effluent and exhaust gas, is especially the reduction of the corrosion of production equipment；Low production cost, safety and environmental protection is, it can be achieved that industrialized production.
Description
Technical field
It is original the present invention relates to graphene and graphene oxide preparation field more particularly to a kind of utilization shrimp and crab shells porous charcoal
Expect graphitizing method.
Background technology
The elements such as H, O, N, formation carbon skeleton are controlling in waste shrimp and crab shells removing raw material on dining table at high temperature
When heating rate and graphitization temperature, main one of the factor for influencing corrosion production equipment corrosion is the graphitizer used.Cause
This, the carbon material that waste is prepared in the case where no graphitizer acts on dining table is generally amorphous carbon, shows in PXRD collection of illustrative plates
Only display Bao Feng；It is difficult to be graphitized at high temperature.
Waste high temperature is graphitized on dining table, generally uses phosphoric acid, the concentrated sulfuric acid, boric acid, KOH, NaOH, ZnCl2, di(2-ethylhexyl)phosphate
Hydrogen potassium, (NH4)2HPO4Deng acquisition porous carbon.Using highly basic, if KOH and NaOH is to industrial equipment graphitizing furnace seriously corroded,
General high temperature furnace has more than is needed several months to be broken with regard to corrosion；Use chloride, such as ZnCl2、CaCl2And FeCl3Not only to industrial production
Equipment graphitizing furnace has corrosiveness, and to environment also toxic gas object dye production environment and air, it is strong to influence the producer
Health and air environment.On the other hand, highly basic is used in the industrial production, and wastewater treatment needs to consume a large amount of warps in production process
Take, production cost can be improved, product price rises；Also influence ecological environment simultaneously.
In recent years, graphene and graphene oxide, due to unique electronics, optically and mechanically performance, causing and holding
Continue and widely pays close attention to.In the exploration of graphene commercial process, people have been devoted to before seeking reproducible carbon source
Drive body and the sustainable production ways of green.
It comes into being in the method that dining table waste shrimp and crab shells charcoal prepares grapheme material as raw material.This method can be effective
The hetero atoms such as N, the P being rich in using dining table waste and special construction improve the physicochemical property of grapheme material so that system
Standby grapheme material shows excellent characteristic in electrochemical field.
Grapheme material is prepared using dining table waste shrimp and crab shells charcoal, not only system considers the heating of dining table waste shrimp and crab shells
Rate and graphitization temperature also mainly consider the use of dining table waste shrimp and crab shells graphitizer in graphitizing process.Section
It using copper as catalyst, polystyrene or polyethylene waste plastic is successfully that carbon source passes through horizontal normal pressure chemical to grind worker
Vapour deposition process has prepared the graphene of single layer, bilayer or even multilayer in tubular type furnace system；The use of graphitizer is useless
The necessary requirement that gurry is converted to graphene.The blade of agriculture and forestry organic waste material green grass can also be prepared under the action of copper catalyst
High quality high-crystallinity single-layer graphene Carbon, 2014,72:66-73; ACS Nano,2011,5(9): 7601-
7607..The petal of lotus flower and shrub althea flower etc. are aided with the temperature less than or equal to 1600 DEG C under argon atmosphere to carry out at thermal spalling
Reason, after removing oxygen containing impurity to greatest extent, can obtain the grapheme material of high quality.Temperature and anaerobic environment are to discarded
It is most important that object prepares grapheme material.Carbon-carbon bond in the cellulose and hemicellulose that are rich in is total to high temperature and anaerobic condition
Division and molecular recombination may be implemented under same-action, finally be able to form graphene.The experiment discovery of graphene is prepared, relatively
High temperature helps to improve the quality of graphene, increase temperature can also effectively remove oxygenate impurity Carbon, 2012,50
(11):4123-4129..The main component of waste shrimp and crab shells is chitosan, the graphitizer and other additives the case where
Synthesis ［ 107758645 A of CN of graphene are realized in lower pyrolysis；.
Use graphite powder to prepare graphene for raw material in existing industrial production graphene technology, using Hummers methods or
Hummers improved methods, need to use a large amount of concentrated sulfuric acids, concentrated nitric acid and potassium permanganate, be generated in this production process a large amount of useless
Water causes huge pollution to environment, consumes huge manpower and financial resources cost so that graphene holds at high price, seriously
Hinder large-scale application and the popularization of graphene.
Invention content
In view of the deficiency of the prior art, the present invention provides a kind of low production cost, and process safety is environmentally friendly, and
Industrialized production can be achieved, utilize the method that shrimp and crab shells porous charcoal is raw graphite.
To achieve the goals above, present invention employs following technical solutions：It is a kind of to utilize shrimp and crab shells porous charcoal for raw material
Graphitizing method includes the following steps：
Step 1, dry shrimp and crab shells porous charcoal is crushed, and sieve of looking over so as to check obtains the porous powdered carbon of shrimp and crab shells；
Step 2, by the porous powdered carbon of shrimp and crab shells obtained by step 1, with graphitization catalyst by weight 1：1~5 mixing, is placed in stone
In Mo Hualu；Under the conditions of nitrogen atmosphere, control graphitizing furnace is warming up to certain temperature, after held for some time, control drop
Temperature arrives room temperature, obtains shrimp and crab shells porous charcoal and is graphitized Primary product；
The porous carbon graphite Primary product of shrimp and crab shells that step 2 obtains is washed repeatedly with dilute hydrochloric acid, then uses deionization by step 3
Water washing is multiple, then using being centrifuged at a high speed, last drying and processing obtains shrimp and crab shells porous charcoal graphene.
Preferably, the shrimp and crab shells porous graphene has clearly the peaks Raman spectrum 2D are clear and legible to recognize, and D/G ＜ 1.
Preferably, the shrimp and crab shells porous charcoal graphene is few layer graphene.
Preferably, the shrimp and crab shells porous charcoal graphene is 3-9 layers.
Preferably, the mesh sieve is 50-100 mesh.
Preferably, the graphitization catalyst is any one or more mixing in potassium carbonate, sodium carbonate and zinc carbonate
It forms.
Preferably, the dilute hydrochloric acid a concentration of 5%.
Preferably, the ultracentrifugal rotating speed is 10000 revs/min.
The present invention also protects the shrimp and crab shells porous charcoal graphene being prepared according to the above method.
Compared with prior art, beneficial effects of the present invention：
（1）The method of the present invention is raw material using resourceful shrimp and crab shells porous charcoal, prepares graphene, obtains high added value electronics
The useful electronic material of industry has high commercial value；
（2）The shrimp and crab shells porous charcoal graphene that the present invention obtains, the peaks Raman spectrum 2D are clear and legible to be recognized, and D/G ＜ 1, meaning
It is few layer graphene shrimp and crab shells porous charcoal graphene, relative to being graphene prepared by raw material with graphite powder, the extent of damage compared with
It is small；Dangerous technique is avoided to have Important Economic value and social value under commercial production conditions；
（3）The present invention mixes graphitization catalyst using any one or more in potassium carbonate, sodium carbonate and zinc carbonate,
Have safer more environmentally friendly relative to a large amount of concentrated sulfuric acids, the conventional graphite alkene production method of concentrated nitric acid and potassium permanganate need to be used
Production technology.
Description of the drawings
Fig. 1 is the high-resolution field emission scanning electron microscope collection of illustrative plates of 1 products therefrom of embodiment.
Specific implementation mode
Below in conjunction with specific embodiment, the present invention is described in detail, but the present invention can be defined by the claims and
The multitude of different ways of covering is implemented.
Embodiment 1
It is a kind of to utilize shrimp and crab shells porous charcoal graphitizing method, include the following steps：
Overnight, then, 50 mesh sieve will be crushed purchased from the drying of the shrimp and crab shells porous charcoal in market；Weigh 100 grams of shrimp and crab shells porous charcoals
It is placed it in graphitizing furnace under the conditions of nitrogen atmosphere with 400 grams of potassium carbonate.Heating rate is controlled, to 1100 DEG C, heat preservation 1 is small
When, after slowly cooling to room temperature, sample is taken out, dilute hydrochloric acid is used（5%）Washing is multiple, is washed with deionized repeatedly, high speed centrifugation
Separation（10000 revs/min）, drying.After tested, products therefrom high-resolution-ration transmission electric-lens collection of illustrative plates is shown in attached drawing [instrument as shown in Figure 1
Device title：High-resolution field emission scanning electron microscope, model：Merlin, manufacturer：German Zeiss companies].
It can be seen from figure 1 that in the present embodiment, clear and legible to recognize in Fig. 1, shrimp and crab shells porous charcoal graphitized products are five layers of stones
Black alkene is also confirmed from Raman collection of illustrative plates.
Embodiment 2
By purchased from the drying of the shrimp and crab shells porous charcoal in market, overnight, then, crushing sieves with 100 mesh sieve；Weigh 100 grams of shrimp and crab shells porous charcoals
It is uniformly mixed with 200 grams of sodium carbonate and 100 grams of zinc carbonates, under the conditions of nitrogen atmosphere, places it in graphitizing furnace.Control heating
After speed is warming up to 1000 DEG C, after slowly cooling to room temperature, sample is taken out, dilute hydrochloric acid is used（10%）Washing is multiple, uses deionized water
Washing is multiple, is centrifuged at a high speed（10000 revs/min）, drying.It is detected through highly transmissive Electronic Speculum；It is close with Fig. 1, obtained graphite
Alkene is 5~7 layers, [instrument title：High-resolution field emission scanning electron microscope, model：Merlin, manufacturer：Germany
Zeiss companies].
Embodiment 3
Overnight, 100 grams of shrimp and crab shells porous charcoals and 200 grams of potassium carbonate and 100 will be weighed purchased from the drying of the shrimp and crab shells porous charcoal in market
Gram sodium carbonate is uniformly mixed, and under the conditions of nitrogen atmosphere, is placed it in graphitizing furnace.Control heating rate is warming up to 1000 DEG C,
After slowly cooling to room temperature, sample is taken out, dilute hydrochloric acid is used（15%）Washing is multiple, is washed with deionized repeatedly, high speed centrifugation
Separation（10000 revs/min）, drying.It is detected through transmission electron microscope；Close with Fig. 1, obtained graphene is 4~8 layers, [instrument name
Claim：High-resolution field emission scanning electron microscope, model：Merlin, manufacturer：German Zeiss companies].
Embodiment 4
By purchased from the drying of the shrimp and crab shells porous charcoal in market, overnight, then, crushing sieves with 100 mesh sieve；Weigh 100 grams of shrimp and crab shells porous charcoals
With 150 grams of sodium carbonate, 150 grams of zinc carbonates and 100 grams of potassium carbonate are uniformly mixed, and under the conditions of nitrogen atmosphere, place it in graphitization
In stove.Control heating rate is warming up to 1100 DEG C, slowly cools to room temperature thickness, takes out sample, use dilute hydrochloric acid（5%）Washing is multiple,
It is washed with deionized repeatedly, is centrifuged at a high speed（10000 revs/min）, drying.It is detected through transmission electron microscope；It is close with Fig. 1,
Obtained graphene is 6~9 layers, [instrument title：High-resolution field emission scanning electron microscope, model：Merlin, manufacturer：
German Zeiss companies].
Embodiment 5：
Overnight, then, 50 mesh sieve will be crushed purchased from the drying of the shrimp and crab shells porous charcoal in market；Weigh 100 grams of shrimp and crab shells porous charcoals
It is uniformly mixed with 500 grams of sodium carbonate, under the conditions of nitrogen atmosphere, places it in graphitizing furnace.Control heating rate is warming up to
1100 DEG C, after slowly cooling to room temperature, sample is taken out, dilute hydrochloric acid is used（8%）Washing is multiple, is washed with deionized repeatedly, high
Speed centrifuges（10000 revs/min）, drying.It is detected through transmission electron microscope；Close with Fig. 1, obtained graphene is 3~8 layers, [instrument
Device title：High-resolution field emission scanning electron microscope, model：Merlin, manufacturer：German Zeiss companies].
The foregoing is merely the preferred embodiments of invention, are not intended to limit the scope of the invention, every to utilize this
It simply changes or converts made by description of the invention content, be applied directly or indirectly in other relevant technical fields, same
Reason is included within the scope of the present invention.
Claims (9)
1. a kind of utilizing the method that shrimp and crab shells porous charcoal is raw graphite, it is characterised in that include the following steps：
Step 1, dry shrimp and crab shells porous charcoal is crushed, and sieve of looking over so as to check obtains the porous powdered carbon of shrimp and crab shells；
Step 2, by the porous powdered carbon of shrimp and crab shells obtained by step 1, with graphitization catalyst by weight 1：1~5 mixing, is placed in stone
In Mo Hualu；Under the conditions of nitrogen atmosphere, control graphitizing furnace is warming up to certain temperature, after held for some time, control drop
Temperature arrives room temperature, obtains shrimp and crab shells porous charcoal and is graphitized Primary product；
The porous carbon graphite Primary product of shrimp and crab shells that step 2 obtains is washed repeatedly with dilute hydrochloric acid, then uses deionization by step 3
Water washing is multiple, then using being centrifuged at a high speed, last drying and processing obtains shrimp and crab shells porous charcoal graphene.
2. a kind of method utilizing shrimp and crab shells porous charcoal as raw graphite according to claim 1, which is characterized in that institute
Stating shrimp and crab shells porous graphene has clearly the peaks Raman spectrum 2D are clear and legible to recognize, and D/G ＜ 1.
3. a kind of method utilizing shrimp and crab shells porous charcoal as raw graphite according to claim 1, which is characterized in that institute
It is few layer graphene to state shrimp and crab shells porous charcoal graphene.
4. telling a kind of method utilizing shrimp and crab shells porous charcoal as raw graphite according to claim 1, which is characterized in that described
Shrimp and crab shells porous charcoal graphene is 3-9 layers.
5. a kind of method utilizing shrimp and crab shells porous charcoal as raw graphite according to claim 1, which is characterized in that institute
It is 50-100 mesh to state mesh sieve.
6. a kind of method utilizing shrimp and crab shells porous charcoal as raw graphite according to claim 1, which is characterized in that institute
It is that any one or more in potassium carbonate, sodium carbonate and zinc carbonate mixes to state graphitization catalyst.
7. a kind of method utilizing shrimp and crab shells porous charcoal as raw graphite according to claim 1, which is characterized in that institute
State dilute hydrochloric acid a concentration of 5%.
8. a kind of method utilizing shrimp and crab shells porous charcoal as raw graphite according to claim 1, which is characterized in that institute
It is 10000 revs/min to state ultracentrifugal rotating speed.
9. the shrimp and crab shells porous charcoal graphene that claim 1-8 any one of them methods are prepared.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111547709A (en) * | 2020-05-09 | 2020-08-18 | 九江学院 | Biomass three-dimensional porous graphene and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105800600A (en) * | 2016-02-29 | 2016-07-27 | 武汉理工大学 | Method for preparing nitrogen self-doped three-dimensional graphene from peels |
| CN107758645A (en) * | 2017-11-20 | 2018-03-06 | 华南理工大学 | A kind of method for preparing grapheme material using discarded object shrimp shell leftover bits and pieces |
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- 2018-05-08 CN CN201810430017.9A patent/CN108545720A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105800600A (en) * | 2016-02-29 | 2016-07-27 | 武汉理工大学 | Method for preparing nitrogen self-doped three-dimensional graphene from peels |
| CN107758645A (en) * | 2017-11-20 | 2018-03-06 | 华南理工大学 | A kind of method for preparing grapheme material using discarded object shrimp shell leftover bits and pieces |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111547709A (en) * | 2020-05-09 | 2020-08-18 | 九江学院 | Biomass three-dimensional porous graphene and preparation method thereof |
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Application publication date: 20180918 |